CN116589609B - Preparation method of phosphorylated nano-chitin based on mechanochemical method and phosphorylated nano-chitin - Google Patents
Preparation method of phosphorylated nano-chitin based on mechanochemical method and phosphorylated nano-chitin Download PDFInfo
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- 229920002101 Chitin Polymers 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000498 ball milling Methods 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 33
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004202 carbamide Substances 0.000 claims abstract description 28
- 239000002244 precipitate Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000376 reactant Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 230000000865 phosphorylative effect Effects 0.000 claims abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims description 55
- 239000011259 mixed solution Substances 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000006366 phosphorylation reaction Methods 0.000 abstract description 23
- 230000026731 phosphorylation Effects 0.000 abstract description 19
- 238000005265 energy consumption Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 238000002791 soaking Methods 0.000 abstract description 4
- 239000007790 solid phase Substances 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 12
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 12
- 238000000265 homogenisation Methods 0.000 description 12
- 235000019837 monoammonium phosphate Nutrition 0.000 description 12
- 239000000835 fiber Substances 0.000 description 9
- 239000006012 monoammonium phosphate Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000000089 atomic force micrograph Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006196 deacetylation Effects 0.000 description 2
- 238000003381 deacetylation reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002078 nanoshell Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009920 food preservation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
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Abstract
The application provides a preparation method of phosphorylated nano-chitin based on a mechanochemical method and phosphorylated nano-chitin, wherein the preparation method comprises the following steps: mixing chitin powder, a phosphorylating reagent and urea, ball milling, and heating the mixed material in the ball milling process to obtain a reactant; and centrifuging and washing reactants, taking a precipitate, and mechanically homogenizing the precipitate to obtain the phosphorylated nano chitin. The chitin is pretreated by the solid-phase mechanochemical method, so that the problems of high water consumption, high energy consumption, environmental pollution and the like existing in the solution soaking method assisted phosphorylation in the current production process are solved.
Description
Technical Field
The application belongs to the technical field of nano chitin preparation, and relates to a preparation method of phosphorylated nano chitin based on a mechanochemical method and phosphorylated nano chitin.
Background
The nano chitin (NChs) is a green and environment-friendly nano material with high crystallinity, high length-diameter ratio, high surface area, low density and rich functional groups, good bioactivity, biocompatibility, degradability and antibacterial property, and is widely applied to the fields of advanced nano materials, tissue engineering, biological medicine and the like.
The traditional nano chitin preparation process comprises an acid hydrolysis method and a TEMPO oxidation or deacetylation combined mechanical treatment method. The acid hydrolysis method and the deacetylation are simple and convenient to operate, but a large amount of strong acid and strong alkali are consumed in the process, so that not only is the difficulty increased for separation and purification operation, but also the water consumption, the energy consumption, the production cost and the environmental pollution are increased. However, the TEMPO reagent has high cost, high corrosiveness and irritation, and washing after oxidation consumes a large amount of water resources, so that the large-scale preparation of nano chitin and the application of the nano chitin in the fields of foods, medicines and the like are limited. The surface modification is widely focused by people as one of important biomass material surface modification methods, and the surface-phosphorylated biomass material not only maintains inherent characteristics, but also is endowed with excellent thermal stability and flame retardant property, so that the surface-phosphorylated biomass material has wide application prospects in the fields of biological medicines, film materials, water treatment, food preservation, flame retardant materials and the like. However, currently, phosphorylation modification has not been used for large-scale preparation of nano-chitin.
Currently, water-based phosphorylation is widely used in the preparation of phosphorylated biomass materials. After the biomass raw material is subjected to solvothermal reaction in an aqueous solution containing phosphate and urea, grafting of phosphate groups can be realized through drying and solidification, and the method has the characteristics of low cost and low toxicity. However, the treatment method of the liquid phase system generally requires a large amount of water resources to achieve a predetermined reaction efficiency, and has problems of long time consumption and high energy consumption in the subsequent drying process.
Disclosure of Invention
Aiming at the defects existing in the prior art, the application aims to provide a preparation method of phosphorylated nano chitin based on a mechanochemical method and phosphorylated nano chitin, wherein the chitin is pretreated by the phosphorylation of a non-liquid phase system of a solid-phase mechanochemical method, so that the problems of high water consumption, high energy consumption, environmental pollution and the like existing in the auxiliary phosphorylation of a solution soaking method in the current production process are solved.
To achieve the purpose, the application adopts the following technical scheme:
in a first aspect, the present application provides a method for preparing phosphorylated nano-chitin based on mechanochemical method, the method comprising:
mixing chitin powder, a phosphorylating reagent and urea, ball milling, and heating the mixed material in the ball milling process to obtain a reactant; and centrifuging and washing reactants, taking a precipitate, and mechanically homogenizing the precipitate to obtain the phosphorylated nano chitin.
The application provides a method for preparing nano chitin by combining mechanical ball milling phosphorylation and high-pressure homogenization nanocrystallization, which aims to pretreat chitin by non-liquid phase system phosphorylation, namely a solid-phase mechanochemical method, and solves the problems of high water consumption, high energy consumption, environmental pollution and the like existing in the prior production process by using a solution soaking method to assist in phosphorylation.
According to the application, the mechanical ball milling is utilized to uniformly mix the chitin, the phosphating reagent and the urea, and meanwhile, the surface phosphorylation is realized, the surface of the fiber is grafted with the charged phosphate group based on the pre-phosphorylation treatment of a non-liquid system, the non-solution system-based phosphorylation pretreatment is simple and convenient to operate, the phosphate group load is high, and the strong electrostatic repulsion caused by the higher electric charge quantity weakens the hydrogen bond interaction between chitin molecular chains, so that the energy consumption and time of the mechanical treatment are reduced, the manpower and material resources are greatly saved, the efficient mechanical homogenization process of the fiber is facilitated, and the prepared phosphorylated nano chitin has better thermal stability and flame retardance.
The application can fully mix reactants in the mixing ball milling process, and can carry out high-temperature curing while carrying out mechanical action on the mixed materials, thereby shortening the preparation time, improving the chemical reaction efficiency and reducing the production energy consumption.
The unit technology based on pre-phosphorylation and high-pressure homogenization is mature and is used for industrial production of partial products, and the method is simple, efficient, energy-saving, environment-friendly, easy to amplify and has good popularization potential and industrial value.
As a preferred embodiment of the present application, the molar ratio of the chitin powder, the phosphorylating agent and the urea is 1 (0.3-1.2): (1.2-4.8), for example, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
The application particularly limits the mole ratio of the chitin powder, the phosphorylating reagent and the urea, and when the addition amount of the phosphorylating reagent is too low, the content of phosphate groups grafted by the chitin is low because the phosphorylating reagent is too low and is difficult to fully react with the chitin; when the addition amount of the phosphorylating agent is too high, degradation of the fibers of chitin may be caused. The urea can play a role in protecting chitin fibers and catalyzing, and when the addition amount of the urea is too low, insufficient phosphorylation reaction of the chitin and self-structure damage and degradation can be caused.
As a preferred embodiment of the present application, the phosphorylating reagent comprises phosphorus pentoxide or a phosphate.
As a preferable technical scheme of the application, the mixed ball milling is carried out in a ball milling device, and the rotating speed of the ball milling device is 600-900rpm, such as 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, 850rpm or 900rpm; the time of the mixing ball milling is 60-150min, for example, 90min, 95min, 100min, 105min, 110min, 115min, 120min, 125min, 130min, 135min, 140min, 145min or 150min, but not limited to the recited values, and other non-recited values in the range of the values are applicable.
The heating temperature in the ball milling process may be 150 to 160℃and may be, for example, 150℃151 ℃, 152 ℃, 153 ℃, 154 ℃, 155 ℃, 156 ℃, 157 ℃, 158 ℃, 159 ℃ or 160 ℃, but is not limited to the values listed, and other values not listed in the range are equally applicable.
The application particularly limits the heating temperature of the ball milling process to 150-160 ℃, and when the heating temperature is lower than 150 ℃, the phosphorylation reaction is insufficient due to the excessively low temperature; when the heating temperature is higher than 160 ℃, phosphate decomposition or degradation of chitin fiber may be caused due to the excessively high temperature.
As a preferable technical scheme of the application, grinding balls are placed in the ball milling device, the grinding balls are divided into first grinding balls and second grinding balls according to different particle size ranges, and the diameter of the first grinding balls is smaller than that of the second grinding balls.
The diameter of the first grinding ball is 1-5mm, for example, 1.0mm, 1.5mm, 2.0mm, 2.5mm, 3.0mm, 3.5mm, 4.0mm, 4.5mm or 5.0mm; the diameter of the second grinding ball is 10-20mm, for example, 10mm, 11mm, 12mm, 13mm, 14mm, 15mm, 16mm, 17mm, 18mm, 19mm or 20mm, but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
If the grinding balls with larger diameters are only used for grinding the raw materials, the large-size raw materials can be crushed due to the larger energy carried by the large-diameter grinding balls, but as the granularity of the raw materials is gradually reduced, the small-size raw materials can be filled into gaps among the large-diameter grinding balls, so that contact points between the grinding balls and the raw materials are reduced, and the refining efficiency is reduced. While the grinding balls with smaller diameters can further refine the raw materials with smaller particle sizes, the grinding balls with smaller carrying energy are insufficient for crushing the raw materials with large sizes, and cannot refine the raw materials. Therefore, the application adopts grinding balls with different diameters to carry out mixed ball milling on the chitin powder according to a certain quantity proportion, so that the chitin powder and the phosphorylating agent can be fully contacted and mixed, and the ball milling efficiency is increased.
As a preferable technical scheme of the application, the number ratio of the first grinding balls to the second grinding balls which are correspondingly placed in each 1 gram of the chitin powder is (5-10): (10-15), and for example, the number ratio can be 5:10, 6:11, 7:12, 8:13, 9:14, 10:15, 5:12, 6:13, 7:15 or 5:10, but is not limited to the recited number, and other non-recited numbers in the numerical range are equally applicable.
The application defines the number ratio of the first grinding ball to the second grinding ball, and can realize the full mixing and grinding of various reactants.
As a preferred embodiment of the present application, the mechanical homogenizing process includes:
dispersing the precipitate in pure water to form a mixed solution, and adjusting the pH value of the mixed solution by using alkali liquor; introducing the mixed solution into a homogenizer, homogenizing at least once under low pressure, and homogenizing at least once under high pressure to form a dispersion; and centrifugally filtering the dispersion liquid to remove the precipitate, thus obtaining the phosphorylated nano chitin.
The application can lead the mixed solution to be initially formed into a more uniform solution by low-pressure homogenization, which is beneficial to the subsequent high-pressure homogenization, and the phosphorylated nano chitin can be obtained by the mechanical action treatment under high pressure after the subsequent high-pressure homogenization.
As a preferred embodiment of the present application, the pH of the mixture is adjusted to 9 to 10 by adding the alkali solution, for example, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9 or 10.0, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The low pressure homogenizing pressure is 100-500Bar, for example, 100Bar, 150Bar, 200Bar, 250Bar, 300Bar, 350Bar, 400Bar, 450Bar or 500Bar; homogenizing under low pressure for 1-5 times may be, for example, 1, 2, 3, 4 or 5 times, but is not limited to the recited values, and other non-recited values within this range are equally applicable.
The high pressure homogenizing pressure is 600-1000Bar, and can be 600Bar, 650Bar, 700Bar, 750Bar, 800Bar, 850Bar, 900Bar, 950Bar or 1000Bar; the homogenization may be performed 7 to 11 times under high pressure, for example, 7 times, 8 times, 9 times, 10 times, or 11 times, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
In a second aspect, the application provides a phosphorylated nano-chitin, which is prepared by the preparation method in the first aspect.
As a preferable technical scheme of the application, the charge amount of the phosphorylated nano chitin is 2.53-4.16mmol/g.
The crystallinity of the phosphorylated nano chitin is 52.3-68.9%.
The application provides a preparation method of phosphorylated nano chitin based on a mechanochemical method, which comprises the following steps:
(1) According to the molar ratio of 1 (0.3-1.2), respectively weighing chitin powder, a phosphorylating reagent and urea, putting the chitin powder, the phosphorylating reagent and the urea into a ball milling device, putting a first grinding ball with the diameter of 1-5mm and a second grinding ball with the diameter of 10-20mm into the ball milling device, wherein the number ratio of the first grinding ball and the second grinding ball which are correspondingly put into each 1 gram of chitin powder is (5-10): (10-15), rotating the ball milling device at the rotating speed of 600-900rpm to mix and ball mill the mixed materials, heating the mixed materials to 150-160 ℃ in the ball milling process, and mixing and ball milling for 60-150min to obtain a reactant;
(2) Dispersing the reactant in 500mL of pure water, taking a precipitate after centrifugal washing for a plurality of times, dispersing the precipitate in the pure water again until the total weight of the mixed solution reaches 500g, and adjusting the pH value of the mixed solution to 9-10 by using 10wt% sodium hydroxide solution;
(3) Introducing the mixed solution into a homogenizer, starting the homogenizer, homogenizing the mixed solution under pressure for 1-5 times under 100-500Bar, homogenizing for 7-11 times after the pressure is increased to 600-1000Bar to form a dispersion, centrifuging the dispersion at a rotating speed of 8000-10000rpm for 1-10min, and removing the precipitate to obtain the phosphorylated nano chitin.
Compared with the prior art, the application has the beneficial effects that:
(1) The application provides a method for preparing nano chitin by combining mechanical ball milling phosphorylation and high-pressure homogenization nanocrystallization, which aims to pretreat chitin by non-liquid phase system phosphorylation, namely a solid-phase mechanochemical method, and solves the problems of high water consumption, high energy consumption, environmental pollution and the like existing in the prior production process by using a solution soaking method to assist in phosphorylation.
(2) According to the application, the mechanical ball milling is utilized to uniformly mix the chitin, the phosphating reagent and the urea, and meanwhile, the surface phosphorylation is realized, the surface of the fiber is grafted with the charged phosphate group based on the pre-phosphorylation treatment of a non-liquid system, the non-solution system-based phosphorylation pretreatment is simple and convenient to operate, the phosphate group load is high, and the strong electrostatic repulsion caused by the higher electric charge quantity weakens the hydrogen bond interaction between chitin molecular chains, so that the energy consumption and time of the mechanical treatment are reduced, the manpower and material resources are greatly saved, the efficient mechanical homogenization process of the fiber is facilitated, and the prepared phosphorylated nano chitin has better thermal stability and flame retardance.
(3) The application can fully mix reactants in the mixing ball milling process, and can carry out high-temperature curing while carrying out mechanical action on the mixed materials, thereby shortening the preparation time, improving the chemical reaction efficiency and reducing the production energy consumption.
(4) The unit technology based on pre-phosphorylation and high-pressure homogenization is mature and is used for industrial production of partial products, and the method is simple, efficient, energy-saving, environment-friendly, easy to amplify and has good popularization potential and industrial value.
Drawings
FIG. 1 is an AFM image of phosphorylated nanoshell prepared in example 1 of the present application;
fig. 2 is a flow chart of a preparation process of the phosphorylated nano-chitin provided in examples 1-10 of the present application.
Detailed Description
The technical scheme of the application is described in detail below with reference to specific embodiments and attached drawings. The examples described herein are specific embodiments of the present application for illustrating the concept of the present application; the description is intended to be illustrative and exemplary in nature and should not be construed as limiting the scope of the application in its aspects. In addition to the embodiments described herein, those skilled in the art can adopt other obvious solutions based on the disclosure of the claims and the specification thereof, including those adopting any obvious substitutions and modifications to the embodiments described herein.
Example 1
The embodiment provides a preparation method of phosphorylated nano chitin, as shown in fig. 2, the preparation method comprises the following steps:
(1) Respectively weighing chitin powder, phosphorus pentoxide and urea according to the molar ratio of 1:0.3:1.2, putting the chitin powder, the phosphorus pentoxide and the urea into a ball milling device, putting a first grinding ball with the diameter of 1mm and a second grinding ball with the diameter of 10mm into the ball milling device, wherein the number ratio of the first grinding ball to the second grinding ball which are correspondingly put into each 1 gram of chitin powder is 5:10, mixing and ball milling the mixed materials by the ball milling device at the rotating speed of 600rpm, heating the mixed materials to 150 ℃ in the ball milling process, and mixing and ball milling for 90min to obtain reactants;
(2) Dispersing the reactant in 500mL of pure water, taking a precipitate after centrifugal washing for a plurality of times, dispersing the precipitate in the pure water again until the total weight of the mixed solution reaches 500g, and adjusting the pH value of the mixed solution to 9 by using 10wt% sodium hydroxide solution;
(3) Introducing the mixed solution into a homogenizer, starting the homogenizer, homogenizing the mixed solution under pressure for 5 times under 500Bar, homogenizing the mixed solution for 11 times after the pressure is increased to 900Bar to form a dispersion, centrifuging the dispersion at 8000rpm for 10min, and removing the precipitate to obtain the phosphorylated nano chitin.
An atomic force microscope image (AFM) of the phosphorylated nano-chitin prepared in this example is shown in fig. 1, and it can be seen from the figure that the phosphorylated nano-chitin is a long rod-shaped nanofiber, and no agglomeration phenomenon exists. The length of the phosphorylated nano chitin can be measured within 200-2000nm by AFM, and the width is less than 50nm. The mechanical ball milling treatment promotes the full mixing and reaction of the chitin powder and the phosphorylating agent, so that more phosphoric acid groups are loaded on the chitin powder, a more efficient mechanical homogenization process is promoted, the energy consumption is saved, and the pollution is reduced.
Example 2
The embodiment provides a preparation method of phosphorylated nano chitin, as shown in fig. 2, the preparation method comprises the following steps:
(1) Respectively weighing chitin powder, phosphorus pentoxide and urea according to the molar ratio of 1:1.2:4.8, putting the chitin powder, the phosphorus pentoxide and the urea into a ball milling device, putting a first grinding ball with the diameter of 2mm and a second grinding ball with the diameter of 13mm into the ball milling device, wherein the number ratio of the first grinding ball to the second grinding ball which are correspondingly put into each 1 gram of chitin powder is 7:12, mixing and ball milling the mixed materials by the ball milling device at the rotating speed of 650rpm, heating the mixed materials to 150 ℃ in the ball milling process, and mixing and ball milling for 90min to obtain reactants;
(2) Dispersing the reactant in 500mL of pure water, taking a precipitate after centrifugal washing for a plurality of times, dispersing the precipitate in the pure water again until the total weight of the mixed solution reaches 500g, and adjusting the pH value of the mixed solution to 9.3 by using 10wt% sodium hydroxide solution;
(3) Introducing the mixed solution into a homogenizer, starting the homogenizer, homogenizing the mixed solution under pressure for 4 times under 300Bar, homogenizing the mixed solution for 10 times after the pressure is increased to 950Bar to form a dispersion, centrifuging the dispersion at a rotating speed of 8500rpm for 7min, and removing the precipitate to obtain the phosphorylated nano chitin.
Example 3
The embodiment provides a preparation method of phosphorylated nano chitin, as shown in fig. 2, the preparation method comprises the following steps:
(1) Respectively weighing chitin powder, monoammonium phosphate and urea according to the molar ratio of 1:1.2:4.8, putting the chitin powder, monoammonium phosphate and urea into a ball milling device, putting a first grinding ball with the diameter of 3mm and a second grinding ball with the diameter of 15mm into the ball milling device, wherein the number ratio of the first grinding ball to the second grinding ball which are correspondingly put into each 1 gram of chitin powder is 8:13, mixing and ball milling the mixed materials by the ball milling device at the rotating speed of 700rpm, heating the mixed materials to 160 ℃ in the ball milling process, and mixing and ball milling for 90min to obtain reactants;
(2) Dispersing the reactant in 500mL of pure water, taking a precipitate after centrifugal washing for a plurality of times, dispersing the precipitate in the pure water again until the total weight of the mixed solution reaches 500g, and adjusting the pH value of the mixed solution to 9.5 by using 10wt% sodium hydroxide solution;
(3) Introducing the mixed solution into a homogenizer, starting the homogenizer, carrying out pressurized homogenization on the mixed solution, homogenizing for 3 times under 100Bar, homogenizing for 9 times after the pressure is increased to 1000Bar to form a dispersion, centrifuging the dispersion at 9000rpm for 5min, and removing the precipitate to obtain the phosphorylated nano chitin.
Example 4
The embodiment provides a preparation method of phosphorylated nano chitin, as shown in fig. 2, the preparation method comprises the following steps:
(1) Respectively weighing chitin powder, monoammonium phosphate and urea according to the molar ratio of 1:0.3:1.2, putting the chitin powder, monoammonium phosphate and urea into a ball milling device, putting a first grinding ball with the diameter of 1mm and a second grinding ball with the diameter of 10mm into the ball milling device, wherein the number ratio of the first grinding ball to the second grinding ball which are correspondingly put into each 1 gram of chitin powder is 5:10, mixing and ball milling the mixed materials by the ball milling device at the rotating speed of 750rpm, heating the mixed materials to 150 ℃ in the ball milling process, and mixing and ball milling for 60min to obtain reactants;
(2) Dispersing the reactant in 500mL of pure water, taking a precipitate after centrifugal washing for a plurality of times, dispersing the precipitate in the pure water again until the total weight of the mixed solution reaches 500g, and adjusting the pH value of the mixed solution to 9.7 by using 10wt% sodium hydroxide solution;
(3) Introducing the mixed solution into a homogenizer, starting the homogenizer, homogenizing the mixed solution under pressure for 5 times under 500Bar, homogenizing the mixed solution for 11 times after the pressure is increased to 900Bar to form a dispersion, centrifuging the dispersion at 8000rpm for 10min, and removing the precipitate to obtain the phosphorylated nano chitin.
Example 5
The embodiment provides a preparation method of phosphorylated nano chitin, as shown in fig. 2, the preparation method comprises the following steps:
(1) Respectively weighing chitin powder, monoammonium phosphate and urea according to the molar ratio of 1:0.3:1.2, putting the chitin powder, monoammonium phosphate and urea into a ball milling device, putting a first grinding ball with the diameter of 1mm and a second grinding ball with the diameter of 10mm into the ball milling device, wherein the number ratio of the first grinding ball to the second grinding ball which are correspondingly put into each 1 gram of chitin powder is 5:10, mixing and ball milling the mixed materials by the ball milling device at the rotating speed of 900rpm, heating the mixed materials to 150 ℃ in the ball milling process, and mixing and ball milling for 150min to obtain reactants;
(2) Dispersing the reactant in 500mL of pure water, taking a precipitate after centrifugal washing for a plurality of times, dispersing the precipitate in the pure water again until the total weight of the mixed solution reaches 500g, and adjusting the pH value of the mixed solution to 10 by using 10wt% sodium hydroxide solution;
(3) Introducing the mixed solution into a homogenizer, starting the homogenizer, homogenizing the mixed solution under pressure for 5 times under 500Bar, homogenizing the mixed solution for 11 times after the pressure is increased to 900Bar to form a dispersion, centrifuging the dispersion at 8000rpm for 10min, and removing the precipitate to obtain the phosphorylated nano chitin.
Example 6
The present embodiment provides a method for preparing phosphorylated nano-chitin, which is different from embodiment 1 in that in step (1), the molar ratio of chitin powder, monoammonium phosphate and urea is adjusted to 1:0.2:1.2, and other process parameters and operation steps are identical to those of embodiment 1.
Example 7
The present embodiment provides a method for preparing phosphorylated nano-chitin, which is different from embodiment 1 in that in step (1), the molar ratio of chitin powder, monoammonium phosphate and urea is adjusted to 1:1:1.2, and other process parameters and operation steps are identical to those of embodiment 1.
Example 8
The present example provides a method for preparing phosphorylated nano-chitin, which is different from example 1 in that in step (1), the molar ratio of chitin powder, monoammonium phosphate and urea is adjusted to 1:0.3:0.8, and other process parameters and operation steps are identical to those of example 1.
Example 9
The present embodiment provides a method for preparing phosphorylated nano chitin, which is different from embodiment 1 in that in step (1), the heating temperature of the mixture is adjusted to 140 ℃, and other process parameters and operation steps are identical to those of embodiment 1.
Example 10
The present embodiment provides a method for preparing phosphorylated nano chitin, which is different from embodiment 1 in that in step (1), the heating temperature of the mixture is adjusted to 170 ℃, and other process parameters and operation steps are identical to those of embodiment 1.
The nano-chitin products prepared in examples 1 to 10 were tested for charge amount by a conductivity titration method, and the nano-chitin products prepared in examples 1 to 10 were tested for crystallinity by an X-ray diffractometer, and the test results are shown in table 1.
TABLE 1
| Charge quantity (mmol/g) | Crystallinity (%) | |
| Example 1 | 3.38 | 56.6 |
| Example 2 | 3.67 | 54.7 |
| Example 3 | 4.16 | 52.3 |
| Example 4 | 3.09 | 58.3 |
| Example 5 | 3.13 | 57.8 |
| Example 6 | 2.98 | 59.4 |
| Example 7 | 2.86 | 61.6 |
| Example 8 | 2.53 | 68.9 |
| Example 9 | 2.80 | 63.8 |
| Example 10 | 2.76 | 65.7 |
As can be seen from the data in Table 1, the charge amounts of the phosphorylated nanoshells prepared in examples 1-5 are higher than those in examples 6-10, but the crystallinity is slightly lower than that in examples 6-10.
As can be seen from comparison of the test data of example 1, example 6 and example 7, the amount of charge of the phosphorylated nano-chitin prepared in example 6 and example 7 is far lower than that of example 1, because the addition amount of ammonium dihydrogen phosphate in example 6 is too low, the ammonium dihydrogen phosphate is difficult to fully react with the chitin, and the content of phosphate groups grafted by the chitin is low, so that the corresponding charge amount is reduced; however, too high addition of ammonium dihydrogen phosphate in example 7 may lead to degradation of chitin fiber, thereby affecting the charge amount of phosphorylated nano-chitin.
As can be seen from comparison of the test data of the embodiment 1 and the embodiment 8, the amount of charge of the phosphorylated nano-chitin prepared in the embodiment 8 is lower than that of the embodiment 1, and the addition amount of urea in the embodiment 8 is too low due to the catalytic effect and the protective effect of urea, so that the phosphorylation reaction of the chitin is insufficient, the structure of the chitin is damaged and degraded, and the amount of charge of the phosphorylated nano-chitin is influenced.
As can be seen from comparison of the test data of example 1, example 9 and example 10, the amount of charge of the phosphorylated nano-chitin prepared in example 9 and example 10 is lower than that of example 1, because the heating temperature in example 9 is too low, resulting in insufficient phosphorylation reaction; however, too high a heating temperature in example 10 would lead to decomposition of phosphate or degradation of chitin fiber, which in turn affects the charge amount of phosphorylated nano-chitin.
The applicant declares that the above is only a specific embodiment of the present application, but the scope of the present application is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present application disclosed by the present application fall within the scope of the present application and the disclosure.
Claims (10)
1. The preparation method of the phosphorylated nano chitin based on the mechanochemical method is characterized by comprising the following steps:
mixing chitin powder, a phosphorylating reagent and urea, ball milling, and heating the mixed material in the ball milling process to obtain a reactant; and centrifuging and washing reactants, taking a precipitate, and mechanically homogenizing the precipitate to obtain the phosphorylated nano chitin.
2. The method according to claim 1, wherein the molar ratio of the chitin powder, the phosphorylating agent and the urea is 1 (0.3-1.2): 1.2-4.8.
3. The method of claim 1, wherein the phosphorylating reagent comprises phosphorus pentoxide or a phosphate.
4. The preparation method according to claim 1, wherein the mixed ball milling is performed in a ball milling device, the rotation speed of the ball milling device is 600-900rpm, and the time of the mixed ball milling is 60-150min;
the heating temperature of the ball milling process is 150-160 ℃.
5. The method according to claim 4, wherein the ball mill is provided with grinding balls, the grinding balls are divided into first grinding balls and second grinding balls according to different particle size ranges, and the diameter of the first grinding balls is smaller than that of the second grinding balls;
the diameter of the first grinding ball is 1-5mm, and the diameter of the second grinding ball is 10-20mm.
6. The method according to claim 5, wherein the number ratio of the first grinding balls to the second grinding balls placed in each 1 g of the chitin powder is (5-10): (10-15).
7. The method of claim 6, wherein the mechanically homogenizing comprises:
dispersing the precipitate in pure water to form a mixed solution, and adjusting the pH value of the mixed solution by using alkali liquor; introducing the mixed solution into a homogenizer, homogenizing at least once under low pressure, and homogenizing at least once under high pressure to form a dispersion; and centrifugally filtering the dispersion liquid to remove the precipitate, thus obtaining the phosphorylated nano chitin.
8. The method according to claim 7, wherein the alkali solution is added to adjust the pH of the mixed solution to 9-10;
the homogenizing pressure of the low pressure is 100-500Bar, and homogenizing is carried out for 1-5 times under the low pressure;
the homogenizing pressure of the high pressure is 600-1000Bar, and the homogenizing is carried out for 7-11 times under the high pressure.
9. A phosphorylated nano-chitin, characterized in that the phosphorylated nano-chitin is prepared by the preparation method of any one of claims 1 to 8.
10. The phosphorylated nano-chitin according to claim 9, wherein the amount of charge of the phosphorylated nano-chitin is 2.53-4.16mmol/g;
the crystallinity of the phosphorylated nano chitin is 52.3-68.9%.
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| CN104017104A (en) * | 2014-05-20 | 2014-09-03 | 江南大学 | Preparation method for soluble and highly substituted phosphorylated yeast glucan |
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| CA2912520C (en) * | 2013-05-16 | 2021-12-14 | Oji Holdings Corporation | Phosphoric acid-esterified fine cellulose fiber and method for producing the same |
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| CN103709268A (en) * | 2013-12-17 | 2014-04-09 | 武汉工程大学 | Method for synthesizing phosphorylated chitin by using methanesulfonic acid as solvent |
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